Azines containing the 5,6-di-hydro-(1,4,2) dioxazine-3-yl group and the use thereof as fungicides

Abstract

The present invention is directed to compounds of having the formula (I) in which G represents a single bond or a grouping  and Z represents alkyl or halogenoalkyl or cycloalkyl or cycloalkylalkyl or heterocyclyl or heterocyclylalkyl or aryl or arylalkyl and L 1 , L 2 , L 3 and L 4 are identical or different and independently of one another in each case represent hydrogen, halogen, cyano, nitro or in each case optionally halogen-substituted alkyl, alkoxy, alkylthio, alkylsulphinyl or alkylsulphonyl having in each case 1 to 6 carbon atoms and in each case optionally substituted by 1 to 5 halogen atoms. The invention also relates to the preparation of such compounds and the use of such compounds to combat plant fungi and plant bacteria.

What is claimed is:  
     
       1. A compound having the formula (I)                    
       in which 
       G represents a single bond or a grouping                    
        wherein  
       R 1  represents hydrogen, or represents alkyl having 1 to 6 carbon atoms, alkenyl having 2 to 6 carbon atoms or alkinyl having 2 to 6 carbon atoms, in each case optionally substituted by halogen or alkoxy having 1 to 4 carbon atoms, or represents cycloalkyl which has 3 to 8 carbon atoms and is optionally substituted by halogen, alkyl or alkoxy having in each case 1 to 4 carbon atoms, or represents arylalkyl which has 1 to 4 carbon atoms in the alkyl part and is optionally substituted in the aryl part, the substituents being chosen from the following list:  
       halogen, cyano, nitro, formyl, carbamoyl, thiocarbamoyl, in each case straight-chain or branched alkyl, alkoxy, alkylthio, alkylsulphinyl or alkylsulphonyl having in each case 1 to 6 carbon atoms, in each case straight-chain or branched alkenyl, alkenyloxy or alkinyloxy having in each case 2 to 6 carbon atoms, in each case straight-chain or branched halogenoalkyl, halogenoalkoxy, halogenoalkylthio, halogenalkylsulphinyl or halogenoalkylsulphonyl having in each case 1 to 6 carbon atoms and 1 to 13 identical or different halogen atoms, in each case straight-chain or branched halogenoalkenyl or halogenoalkenyloxy having in each case 2 to 6 carbon atoms and 1 to 11 identical or different halogen atoms, in each case straight-chain or branched alkylamino, dialkylamino, alkylcarbonyl, alkylcarbonyloxy, alkoxycarbonyl, alkylsulphonyloxy, hydroximinoalkyl or alkoximinoalkyl having in each case 1 to 6 carbon atoms in the individual alkyl parts, in each case divalent alkylene or dioxyalkylene which has in each case 1 to 6 carbon atoms and is in each case optionally monosubstituted or polysubstituted in an identical or different manner by halogen and/or straight-chain or branched alkyl having 1 to 4 carbon atoms and/or straight-chain or branched halogenoalkyl having 1 to 4 carbon atoms and 1 to 9 identical or different halogen atoms,  
       R represents alkyl having 1 to 4 carbon atoms, or cycloalkyl which has 3 to 6 carbon atoms and is optionally mono- to tetrasubstituted by halogen or alkyl,  
       Z represents alkyl or halogenoalkyl which has in each case 1 to 4 carbon atoms and is in each case optionally monosubstituted by cyano or alkoxy;  
       represents cycloalkyl or cycloalkylalkyl which has in each case 3 to 7 carbon atoms in the cycloalkyl part and 1 to 4 carbon atoms in the alkyl part and is in each case optionally monosubstituted to tetrasubstituted by halogen or alkyl;  
       represents heterocyclyl or heterocyclylalkyl which has in each case 3 to 7 ring members and 1 to 4 carbon atoms in the alkyl part and is optionally substituted by halogen or alkyl having 1 to 4 carbon atoms, wherein said heterocyclyl or said heterocyclylalkyl is selected from the group consisting of a saturated cyclic compound, an unsaturated cyclic compound and an aromatic cyclic compound in which at least one ring member is a heteroatom, wherein said heteroatom is selected from the group consisting of oxygen, nitrogen and sulfur with the proviso that where said cyclic compound contains more than one oxygen atom said oxygen atoms are not adjacent, and optionally wherein said cyclic compound forms a polycyclic ring system, optionally with additional cyclic compounds selected from the group consisting of carbocyclic and heterocyclic compounds, wherein said additional heterocyclic compounds are as defined above, and wherein said polycyclic ring system includes rings selected from the group consisting of fused-on and bridged rings, said polycyclic ring system preferably being selected from the group consisting of mono-ring aromatic ring systems and bicyclic aromatic ring systems;  
       or represents aryl or arylalkyl which has in each case 6 to 10 carbon atoms in the aryl part and 1 to 4 carbon atoms in the alkyl part and is in each case optionally monosubstituted to tetrasubstituted in an identical or different manner in the aryl part, the possible substituents preferably being chosen from the following list:  
       halogen, cyano, nitro, amino, formyl, carbamoyl, thiocarbamoyl;  
       in each case straight-chain or branched alkyl, alkoxy, alkoxyalkyl, alkylthioalkyl, alkylaminoalkyl, dialkylaminoalkyl, alkylthio, alkylsulphinyl or alkylsulphonyl having in each case 1 to 8 carbon atoms;  
       in each case straight-chain or branched alkenyl or alkenyloxy having in each case 2 to 6 carbon atoms;  
       in each case straight-chain or branched halogenoalkyl, halogenoalkoxy, halogenoalkylthio, halogenoalkylsulphinyl or halogenoalkylsulphonyl having in each case 1 to 6 carbon atoms and 1 to 13 identical or different halogen atoms;  
       in each case straight-chain or branched halogenoalkenyl or halogenoalkenyloxy having in each case 2 to 6 carbon atoms and 1 to 11 identical or different halogen atoms;  
       in each case straight-chain or branched alkylamino, dialkylamino, alkylcarbonyl, alkylaminocarbonyl, diakylaminocarbonyl, arylakylaminocarbonyl, alkenylcarbonyl or alkinylcarbonyl having 1 to 6 carbon atoms and in the particular hydrocarbon chains;  
       cycloalkyl or cycloalkyloxy having in each case 3 to 6 carbon atoms;  
       in each case divalent alkylene having 3 or 4 carbon atoms, oxyalkylene having 2 or 3 carbon atoms or dioxyalkylene having 1 or 2 carbon atoms, in each case optionally monosubstituted to tetrasubstituted in an identical or different manner by fluorine, chlorine, oxo, methyl, trifluoromethyl or ethyl;  
       or a grouping                    
        wherein  
       A 1  represents hydrogen or alkyl having 1 to 4 carbon atoms or cycloalkyl having 3 to 6 carbon atoms and  
       A 2  represents hydroxyl, amino, methylamino, methyl, phenyl, benzyl, alkoxy, alkylamino or dialkylamino having 1 to 4 carbon atoms in the particular alkyl chains and  
       L 1 , L 2 , L 3  and L 4  are identical or different and independently of one another in each case represent hydrogen, halogen, cyano, nitro or in each case optionally halogen-substituted alkyl, alkoxy, alkylthio, alkylsulphinyl or alkylsulphonyl having in each case 1 to 6 carbon atoms and in each case optionally substituted by 1 to 5 halogen atoms.  
     
     
       2. The compound of the formula (I) according to  claim 1 , in which 
       G represents a single bond.  
     
     
       3. The compound of the formula (I) according to  claim 1 , in which 
       G represents a grouping                    
     
     
       4. The compounds of the formula (I) according to  claim 1 , in which 
       R represents methyl, ethyl, n- or i-propyl, or represents cyclopropyl, cyclobutyl or cyclopentyl, in each case optionally monosubstituted to tetrasubstituted by fluorine, chlorine, methyl or ethyl, in particular represents methyl.  
     
     
       5. The compounds of the formula (I) according to  claim 1 , in which 
       G represents a single bond and  
       Z represents cyclopentyl or cyclohexyl, in each case optionally monosubstituted to tetrasubstituted by fluorine, chlorine, methyl or ethyl;  
       represents thienyl, pyridyl, furyl, thienylmethyl, pyridylmethyl, benzopyrazolyl or furylmethyl, optionally substituted by methyl, ethyl, fluorine, chlorine or bromine;  
       or represents benzyl, 1-phenylethyl or 2-phenylethyl, in each case optionally monosubstituted to tetrasubstituted in an identical or different manner, in particular substituted phenyl, the possible substituents preferably being chosen from the following list:  
       fluorine, chlorine, bromine, cyano, nitro, amino, formyl, carbamoyl, thiocarbamoyl, methyl, ethyl, n- or i-propyl, n-, i-, s- or t-butyl, methoxymethyl, methoxy, ethoxy, n- or i-propoxy, methylthio, ethylthio, n- or i-propylthio, methylsulphinyl, ethylsulphinyl, methylsulphonyl or ethylsulphonyl, methylaminomethyl, dimethylaminomethyl, vinyl, allyl, 2-methylallyl, propen-1-yl, crotonyl, propargyl, vinyloxy, allyloxy, 2-methylallyloxy, propen-1-yloxy, crotonyloxy, propargyloxy;  
       trifluoromethyl, trifluoroethyl, difluoromethoxy, trifluoromethoxy, difluorochloromethoxy, trifluoroethoxy, pentafluoroethoxy, 2-chloro-1,1,2-trifluoroethoxy, difluoromethylthio, trifluoromethylthio, difluorochloromethylthio, trifluoromethylsulphinyl or trifluoromethylsulphonyl, methylamino, ethylamino, n- or i-propylamino, dimethylamino, diethylamino, acetyl, propionyl, methoxycarbonyl, ethoxycarbonyl, methylaminocarbonyl, ethylaminocarbonyl, dimethylaminocarbonyl, diethylaminocarbonyl, acryloyl, propioloyl, cyclopentyl, cyclohexyl, or in each case divalent propanediyl, ethyleneoxy, methylenedioxy or ethylenedioxy, in each case optionally monosubstituted to tetrasubstituted in an identical or different manner by fluorine, chlorine, oxo, methyl or trifluoromethyl,  
       or a grouping                    
        wherein  
       A 1  represents hydrogen or methyl and  
       A 2  represents hydroxyl, methoxy, ethoxy, amino, methylamino, methyl, phenyl or benzyl.  
     
     
       6. The compounds of the formula (I) according to  claim 1 , in which 
       G represents the grouping                    
        and  
       Z represents methyl, ethyl, n- or i-propyl, n-, i-, s- or t-butyl or trifluoromethyl, or represents cyclopentyl or cyclohexyl, in each case optionally monosubstituted to tetrasubstituted by fluorine, chlorine, methyl or ethyl;  
       represents thienyl, pyridyl, furyl, thienylmethyl, pyridylmethyl or furylmethyl, optionally substituted by methyl, ethyl, fluorine, chlorine or bromine;  
       or represents benzyl, 1-phenylethyl or 2-phenylethyl, in each case optionally monosubstituted to tetrasubstituted in an identical or different manner, in particular substituted phenyl, the possible substituents preferably being chosen from the following list:  
       fluorine, chlorine, bromine, cyano, nitro, amino, formyl, carbamoyl, thiocarbamoyl, methyl, ethyl, n- or i-propyl, n-, i-, s- or t-butyl, methoxymethyl, methoxy, ethoxy, n- or i-propoxy, methylthio, ethylthio, n- or i-propylthio, methylsulphinyl, ethylsulphinyl, methylsulphonyl or ethylsulphonyl, methylaminomethyl, dimethylaminomethyl, vinyl, allyl, 2-methylallyl, propen-1-yl, crotonyl, propargyl, vinyloxy, allyloxy, 2-methylallyloxy, propen-1-yloxy, crotonyloxy, propargyloxy;  
       trifluoromethyl, trifluoroethyl, difluoromethoxy, trifluoromethoxy, difluorochloromethoxy, trifluoroethoxy, pentafluoroethoxy, 2-chloro-1,1,2-trifluoroethoxy, difluoromethylthio, trifluoromethylthio, difluorochloromethylthio, trifluoromethylsulphinyl or trifluoromethylsulphonyl, methylamino, ethylamino, n- or i-propylamino, dimethylamino, diethylamino, acetyl, propionyl, methoxycarbonyl, ethoxycarbonyl, methylaminocarbonyl, ethylaminocarbonyl, dimethylaminocarbonyl, diethylaminocarbonyl, acryloyl, propioloyl, cyclopentyl, cyclohexyl, or in each case divalent propanediyl, ethyleneoxy, methylenedioxy or ethylenedioxy, in each case optionally monosubstituted to tetrasubstituted in an identical or different manner by fluorine, chlorine, oxo, methyl or trifluoromethyl,  
       or a grouping                    
        wherein  
       A 1  represents hydrogen or methyl and  
       A 2  represents hydroxyl, methoxy, ethoxy, amino, methylamino, methyl, phenyl or benzyl.  
     
     
       7. The compounds of the formula (I) according to  claim 1 , in which 
       L 1 , L 2 , L 3  and L 4  are identical or different and independently of one another in each case represent hydrogen, fluorine, chlorine, bromine, cyano, nitro, methyl, ethyl, n- or i-propyl, n-, i-, s- or t-butyl, methoxy, ethoxy, n- or i-propoxy, methylthio, ethylthio, methylsulphinyl, ethylsulphinyl, methylsulphonyl or ethylsulphonyl, trifluoromethyl, trifluoroethyl, difluoromethoxy, trifluoromethoxy, difluorochloromethoxy, trifluoroethoxy, difluoromethylthio, difluorochloromethylthio, trifluoromethylthio, trifluoromethylsulphinyl or trifluoromethylsulphonyl, preferably hydrogen or methyl, and in particular hydrogen.  
     
     
       8. The compounds of the formula (I) according to  claim 1 , in which 
       G represents a single bond.  
     
     
       9. A fungicidal composition, characterized by a content of at least one compound of the formula (I) according to  claim 1 . 
     
     
       10. A method of combating fungi comprising the step of applying a fungicidally effective amount of a compound of the formula (I) according to  claim 1  to a member selected from the group consisting of said fungi, an environment of said fungi, and combinations thereof. 
     
     
       11. A process for the preparation of compounds of the formula (I) as defined in  claim 1  comprising reacting 
       a) ketones of the formula (II)                    
        in which  
       G, R and Z have the meanings given in  claim 1 ,  
       with an aldehyde of the formula (III)                    
       in which 
       L 1 , L 2 , L 3  and L 4  have the meanings given in  claim 1 ,  
       and hydrazine or hydrazine hydrate, 
       optionally in the presence of a diluent and optionally in the presence of a catalyst, or reacting 
       b) hydrazones of the formula (IV)                    
        in which  
       G, R and Z have the meanings given in  claim 1 , are reacted with an aldehyde of the formula (III), optionally in the presence of a diluent and optionally in the presence of a catalyst, or reacting  
       c) hydrazine derivatives of the formula (V)                    
        in which  
       L 1 , L 2 , L 3  and L 4  have the meanings given in  claim 1 ,  
       with a ketone of the formula (II), optionally in the presence of a diluent and optionally in the presence of a catalyst. 
     
     
       12. A compound having the formula (III)                    
       in which 
       L 1 , L 2 , L 3  and L 4  have the meanings given in  claim 1 .  
     
     
       13. A compound having the formula (I) according to  claim 1 , in which 
       G represents a grouping                    
        wherein  
       R represents hydrogen, methyl, ethyl, n- or i-propyl, n-, i- or s-butyl, allyl, propargyl or but-2-en-1-yl.  
     
     
       14. The compounds of  claim 1 , wherein L 1 , L 2 , L 3  and L 4  are identical or differently and independently of one another in each case represent hydrogen or methyl.